EP0560495A1 - Wärmeschrumpfbarer Mehrschichtfilm - Google Patents

Wärmeschrumpfbarer Mehrschichtfilm Download PDF

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Publication number
EP0560495A1
EP0560495A1 EP93300972A EP93300972A EP0560495A1 EP 0560495 A1 EP0560495 A1 EP 0560495A1 EP 93300972 A EP93300972 A EP 93300972A EP 93300972 A EP93300972 A EP 93300972A EP 0560495 A1 EP0560495 A1 EP 0560495A1
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EP
European Patent Office
Prior art keywords
laminate film
ethylene
copolymer
film
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93300972A
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English (en)
French (fr)
Other versions
EP0560495B1 (de
Inventor
Teruo Tada
Hideyuki Yamashita
Kazuo Kondo
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Okura Industrial Co Ltd
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Okura Industrial Co Ltd
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Publication of EP0560495A1 publication Critical patent/EP0560495A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2813—Heat or solvent activated or sealable
    • Y10T428/2817—Heat sealable
    • Y10T428/2826—Synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31739—Nylon type
    • Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to a laminate film and, more specifically, to a heat shrinkable, laminated film having excellent gas barrier properties.
  • US-A-4,726,984 discloses a five-layer film composed of a core layer of an ethylene-vinyl alcohol copolymer, two outer layers of a blend of polypropylene and ethylene-propylene copolymer, and two intermediate adhesive layers disposed between the core layer and the respective outer layers. While this film permits high speed, automatic package, the heat sealability and gas barrier properties thereof are not satisfactory. In particular, this film requires a specific narrow range of temperature to perform heat sealing and does not provide a high seal strength. Further, when this film is subjected to repeated bending, pin holes are formed to the extent that the gas barrier properties thereof are damaged.
  • US-A-4,547,433 discloses a five-layer film composed of a core layer of an ethylene-vinyl alcohol copolymer, two outer layers one of which is formed of an ethylene-alpha-olefin copolymer and/or an ethylene- vinyl acetate copolymer and the other one of which is formed of a cross-linked product of the above copolymer, and two intermediate, adhesive layers disposed between the core layer and the respective outer layers. While this film has good gas barrier properties, the toughness is not satisfactory so that breakage or elongation is apt to occur during packaging operations. Further, cross-linking of the outer layer is essential in order to smoothly perform stretching. Cross-linking is, however, undesirable because heat-sealability is adversely affected and because the crosslinked film cannot be melted and, therefore, cannot be reused.
  • a heat-shrinkable laminate film comprising:
  • An unoriented laminate film from which the heat-shrinkable laminate film according to the present invention is to be produced does not require any cross-linking treatment. Nonetheless, the unoriented film may be easily stretched to provide the heat-shrinkable laminate film having excellent heat shrinkability. Moreover, the laminate film thus obtained exhibits good heat sealability and gas barrier properties and has sufficient toughness and, thus, is suited for use in high speed automatic packaging.
  • FIGURE is a sectional view schematically illustrating a laminate film according to the present invention.
  • a core, gas-barrier layerformed of an ethylene-vinyl alcohol copolymer designated as 1 is a core, gas-barrier layerformed of an ethylene-vinyl alcohol copolymer.
  • the ethylene-vinyl alcohol copolymer is preferably one which is obtained by saponifying an ethylene-vinyl acetate copolymer having an ethylene comonomer content of 25-50 mole % with a a saponification degree of 95 % or more.
  • the core layer 1 may also contain a resin compatible with the ethylenevinyl alcohol copolymer, such as a polyamide or an ethylenevinyl acetate copolymer, in such an amount that the gas barrier properties thereof are not adversely affected.
  • the thickness of the core layer 1 is preferably 1 -10 f..lm, more preferably 2-6 f..lm, for reasons of optimum gas barrier properties.
  • Each of the intermediate layers 2a and 2b includes a propylene copolymer which contains propylene as major monomer units and which is selected from (a) copolymers of an unsaturated carboxylic acid or a derivative thereof and propylene and (b) copolymers of an unsaturated carboxylic acid or a derivative thereof and an alpha- olefin-propylene copolymer containing not greater than 10 % by weight of alpha-olefin comonomer.
  • a propylene copolymer which contains propylene as major monomer units and which is selected from (a) copolymers of an unsaturated carboxylic acid or a derivative thereof and propylene and (b) copolymers of an unsaturated carboxylic acid or a derivative thereof and an alpha- olefin-propylene copolymer containing not greater than 10 % by weight of alpha-olefin comonomer.
  • the propylene copolymer is preferably a graft copolymer obtained by grafting the unsaturated carboxylic acid or derivative thereof on polypropylene homopolymers or alphaolefin-propylene copolymers.
  • the alpha-olefin may be, for example, ethylene or 1-butene.
  • the amount of the alpha-olefin in the alpha-olefin-propylene copolymer should be 10 % by weight or less since otherwise the unoriented laminate film is unable to be uniformly stretched and, further, the stretched laminate film becomes ill-suited for high speed automatic packaging.
  • the derivatives of the unsaturated carboxylic acid include, for example, an anhydride, an ester and an amide.
  • suitable unsaturated acids and derivatives thereof are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylic anhydride, methacrylic anhydride, maleic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, monomethyl ester of maleic acid, monoethyl ester of maleic acid, acrylamide and methacrylamide.
  • the content of the unsaturated carboxylic acid or derivative thereof in the propylene copolymer is preferably 0.1-2 % by weight.
  • the total thickness of the intermediate layers 2a and 2b is preferably 10-60 %, more preferably 20-50 % of the total thickness of the heat-shrinkable laminate film for reasons of good stretchability, toughness and shrinkability.
  • the total thickness of the intermediate layers 2a and 2b is below 10 %, it becomes difficult to stretch the unoriented raw film in a stable manner. Further, the stretched film fails to exhibit significantly improved toughness and heat shrinking speed.
  • the total thickness of the intermediate layers 2a and 2b exceeds 60 %, pin holes tend to be formed during use of the heat-shrinkable laminate film so that the gas barrier properties thereofare deteriorated. Further, the laminate film fails to exhibit significantly improved heat seal strength.
  • the respective surfaces of said intermediate layers 2a and 2b opposite the core layer 1 are provided with outer layers 3a and 3b each including an ethylene polymer.
  • the ethylene polymer is a polymer containing ethylene as major component and may be a polyethylene homopolymer or a copolymer of ethylene such as an ethylene-alpha-olefin copolymer, an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer.
  • the use of a straight chain co- polymer which is composed of ethylene and an alpha- olefin having 4-8 carbon atoms and which has a specific gravity of 0.900-0.930 is particularly preferred.
  • the outer layers 3a and 3b may contain one or more additives such as anti-static agent, a lubricant, a heat stabilizer and a moisture deposition-preventing agent.
  • the heat-shrinkable laminate film according to the present invention may be prepared in any conventionally known method. For example, using three extruders and a five layered die, an ethylene-vinyl alcohol copolymer, a propylene copolymer and an ethylene polymer are coextruded to obtain an extruded five-layerfilm. The extruded film is rapidly cooled and is then stretched. When the stretching is performed by an inflation method, the above coextrusion is performed using a circular die to obtain a tubular extruded film. The stretching is performed at an elevated temperature uniaxially or biaxially using a tenter stretching device in the case of sheet-like film or an inflation stretching device in the case of a tubularfilm.
  • Biaxial stretching is preferred when the laminate film is used for packaging articles by heat-shrink packaging.
  • the stretching ratio is generally 2.5-5.0 in each of the longitudinal and transverse directions.
  • the unoriented laminate film which uses a propylene copolymer for forming the intermediate adhesive layers shows good processability in stretching.
  • the resulting stretched, heat-shrinkable laminate film generally has a thickness of 10-50 f..lm.
  • the laminate film has high toughness and high heat-shrinking speed so that it is very suited for high speed, automatic heat-shrink packaging.
  • the use of a non- crosslinked ethylene polymer as the outer layers gives improved heat-sealability and resistance to pinholes formation.
  • the resulting laminate film becomes poor in toughness and slow in heat-shrinking speed though an improved inter-layer adhesion strength is obtainable.
  • Sample film (200 mm x 280 mm) is shaped into a cylindrical form.
  • One end of the cylindrical film is fixed to a twist-reciprocating member of a testing machine with the other end thereof being fixed to a stator.
  • the twist-reciprocating member is adapted to reciprocate between first and second positions and rotate through 360° during its movement toward the stator (from the first position to the second position) and rotate in a reverse direction during its movement in the direction apart from the stator (from the second position to the first position).
  • the machine is then operated to perform 2,000 reciprocations.
  • the number of pin holes formed as a result of the test is counted.
  • a box is packaged with sample film while sealing with a hot seal plate at various sealing temperatures of (100 + 1 0n)°C, wherein n is an integer of O or more.
  • the temperature range which can provide a seal strength of 200 g/cm or more is measured.
  • sample film is sealed at a temperature which can provide optimum seal strength.
  • the sealed film is cut into a tape having a width of 1 cm such that the sealed portion is oriented transversely.
  • the tape is attached to a tensile testing machine and drawn at a rate of 300 mm/min until the tape is broken at the sealed portion. The maximum strength required to break the seal portion is measured.
  • the tubular extruded film was rapidly cooled to room temperature and then subjected to inflation biaxial stretching at a stretching temperature of 120 °C, stretching ratios of 3.5 in the longitudinal (machine) direction and 3.5 in transverse direction, and longitudinally cut to obtain a thermally shrinkable laminate film having thicknesses of C/B/A/B/C layers of 10/4/2/4/10 (wm), respectively.
  • the total thickness of the intermediate layers B was thus about 27 % (8/30 x 100 %) of the total thickness of the laminate film.
  • the stretching was able to be continuously carried out in a stable manner for a long period of time.
  • Foamed trays 120 mm x 210 mm x 20 mm
  • the packages were continuously passed through a heater tunnel with a residence time of 4 seconds to effect heat shrinkage. No troubles were caused during packing with the pillow packaging machine.
  • the film was found to be completely shrunk during the passage through the tunnel.
  • the laminate film was further tested to reveal that the number of pin holes was zero, the temperature range suitable for heat sealing was between 130 and 200 °C, the strength of heat seal was 600 g/cm and the Young's modulus was 6,000 kg/cm 2 .
  • Example 1 was repeated in the same manner as described except that the maleic anhydride-grafted propylene-ethylene copolymer (ethylene content: 2 % by weight) was replaced by a maleic anhydride-grafted polyethylene for forming each of the intermediate layers. It was found that the stretching was not able to be continuously performed for a long period of time. In the continuous automatic packaging, the film was tend to be caught by the former of the pillow packaging machine to cause breakage of the film. Further, the heat shrinkage was not completed within the 4 seconds heat treatment so that slack packages resulted. The Young's modulus of the film was 3,000 kg/cm 2 .
  • Example 1 was repeated in the same manner as described except that the low density polyethylene (ethylene-hexene copolymer having a hexene content of 6 mole %) was replaced by an ethylene-propylene copolymer having an ethylene content of 3 % by weight for forming each of the outer layers.
  • the stretching was able to be continuously carried out in a stable manner for a long period of time. No troubles were caused during packing with the pillow packaging machine.
  • the film was found to be completely shrunk during the passage through the tunnel. However, the film was found to have problems in resistance to pin hole formation and heat seal strength. Namely, the tests revealed that the number of pin holes was 5, the temperature range suitable for heat sealing was between 150 and 200 °C, the strength of heat seal was 300 g/cm and the Young's modulus was 11,000 kg/cm 2 .
  • Example 1 was repeated in the same manner as described except that the maleic anhydride-grafted propylene-ethylene copolymer (ethylene content: 2 % by weight) was replaced by a maleic anhydride-grafted propylene-butylene copolymer (butylene content: 15 % by weight) for forming each of the intermediate layers. It was found that the stretching was not able to be continuously performed for a long period of time. The Young's modulus of the film was 4,000 kg/cm2.
  • Example 1 was repeated in the same manner as described except that the thicknesses of the layers of the C/B/A/B/C film were changed to 12/2/2/2/12.
  • the total thickness of the intermediate layers B was thus about 13 % (4/30 x 100 %).
  • the stretching was able to performed continuously for a long period of time but in a less stable manner in comparison with that in Example 1.
  • the film permitted high speed automatic shrink packaging without no substantial troubles.
  • the appearance of the packages was inferiorto that in Example 1, however. Tests revealed that the temperature range suitable for heat sealing was between 130 and 200 °C, the strength of heat seal was 650 g/cm and the Young's modulus was 4,000 kg/cm 2 .
  • Example 1 was repeated in the same manner as described except that the thicknesses of the layers of the C/B/A/B/Cfilm were changed to 6/8/2/8/6.
  • the total thickness of the intermediate layers B was thus about 53 % (16/30 x 100 %).
  • the stretching was able to performed continuously for a long period of time likewise in Example 1.
  • the film permitted high speed automatic shrink packaging without no troubles.
  • the appearance of the packages was comparable to that in Example 1. Tests revealed that the temperature range suitable for heat sealing was between 130 and 200 °C, the strength of heat seal was 400 g/cm and the Young's modulus was 9,000 kg/cm 2 . Thus, the heat seal strength was much inferior in comparison with that in Example 1.

Landscapes

  • Laminated Bodies (AREA)
  • Containers And Plastic Fillers For Packaging (AREA)
  • Wrappers (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
EP93300972A 1992-03-13 1993-02-10 Wärmeschrumpfbarer Mehrschichtfilm Expired - Lifetime EP0560495B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP04089377A JP3104885B2 (ja) 1992-03-13 1992-03-13 熱収縮性積層フィルム
JP8937792 1992-03-13
JP89377/92 1992-03-13

Publications (2)

Publication Number Publication Date
EP0560495A1 true EP0560495A1 (de) 1993-09-15
EP0560495B1 EP0560495B1 (de) 2000-11-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93300972A Expired - Lifetime EP0560495B1 (de) 1992-03-13 1993-02-10 Wärmeschrumpfbarer Mehrschichtfilm

Country Status (6)

Country Link
US (1) US5318829A (de)
EP (1) EP0560495B1 (de)
JP (1) JP3104885B2 (de)
AU (1) AU653889B2 (de)
DE (1) DE69329703T2 (de)
ES (1) ES2152942T3 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0673759A3 (de) * 1994-03-22 1996-07-03 Grace W R & Co Hochorientierter Mehrschichtfilm.
WO2002053377A1 (en) * 2000-12-29 2002-07-11 A.W.A.X. Progettazione E Ricerca S.R.L. Barrier stretch film particularly for the packaging of food products and method for the production thereof
WO2005108069A1 (en) * 2004-05-07 2005-11-17 A.W.A.X. Progettazione E Ricerca S.R.L. Extensible multilayer film

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2106258C (en) * 1992-09-18 2003-11-04 Gautam P. Shah Moisture barrier film
RU2133702C1 (ru) 1993-04-09 1999-07-27 Вискейз Корпорейшн Многослойная пленка для упаковки сыра, упаковка и способ ее изготовления
US5382470A (en) 1993-04-09 1995-01-17 Viskase Corporation EVOH oxygen barrier stretched multilayer film
US6964798B2 (en) 1993-11-16 2005-11-15 Baxter International Inc. Multi-layered polymer based thin film structure for medical grade products
EP0744285B1 (de) * 1995-05-24 1999-12-15 Cryovac, Inc. Mehrschichtiger Verpackungsfilm mit Saurstoffbarriere
IT1282672B1 (it) * 1996-02-23 1998-03-31 Grace W R & Co Pellicole di materiale termoplastico con proprieta' barriera ai gas
US6083587A (en) 1997-09-22 2000-07-04 Baxter International Inc. Multilayered polymer structure for medical products
DE19835745A1 (de) 1998-08-07 2000-02-17 Wolff Walsrode Ag Gasdichte Kaschierfolie und daraus hergestellte Packstoffe
US6302321B1 (en) 1999-10-11 2001-10-16 Sonoco Development, Inc. Sealant layer for container lid
DE10018049A1 (de) 2000-04-12 2001-10-25 Wolff Walsrode Siegelbare Kaschierfolie mit Antibeschlageigenschaften und Sauerstoffbarriere sowie ein diese Folie enthaltendes Verpackungsmaterial
MXPA06011837A (es) 2004-04-27 2007-01-16 Baxter Int Sistema de reactor de tanque agitado.
US7517569B2 (en) * 2005-06-06 2009-04-14 Cryovac, Inc. Shrink packaging barrier film
JP2009083165A (ja) * 2007-09-28 2009-04-23 Dainippon Printing Co Ltd 易開封性及び酸素バリア性を有する多層積層フィルム
EP3429044B1 (de) * 2017-07-14 2023-10-18 Tyco Electronics Raychem GmbH Wärmeschrumpfbares bauteil und verfahren zum zusammenbau eines wärmeschrumpfbaren bauteils
CN114867602A (zh) 2020-01-06 2022-08-05 因夫聚丙烯有限责任公司 包括阻隔层的聚合物基底

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US4547433A (en) * 1981-11-11 1985-10-15 Kureha Kagaku Kogyo Kabushiki Kaisha Heat-shrinkable laminate film
EP0236099A2 (de) * 1986-02-28 1987-09-09 W.R. Grace & Co.-Conn. Verpackungssauerstoffsperrfilm
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US5645788A (en) * 1992-11-03 1997-07-08 W.R. Grace & Co.-Conn. Making highly oriented multilayer film
EP0673759A3 (de) * 1994-03-22 1996-07-03 Grace W R & Co Hochorientierter Mehrschichtfilm.
AU700179B2 (en) * 1994-03-22 1998-12-24 Cryovac, Inc. Highly oriented multilayer film
WO2002053377A1 (en) * 2000-12-29 2002-07-11 A.W.A.X. Progettazione E Ricerca S.R.L. Barrier stretch film particularly for the packaging of food products and method for the production thereof
WO2005108069A1 (en) * 2004-05-07 2005-11-17 A.W.A.X. Progettazione E Ricerca S.R.L. Extensible multilayer film

Also Published As

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EP0560495B1 (de) 2000-11-29
AU3316493A (en) 1993-09-16
DE69329703D1 (de) 2001-01-04
JP3104885B2 (ja) 2000-10-30
US5318829A (en) 1994-06-07
AU653889B2 (en) 1994-10-13
ES2152942T3 (es) 2001-02-16
DE69329703T2 (de) 2001-05-10
JPH05254076A (ja) 1993-10-05

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